Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09D133/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

• the present invention relates to a CO 2 abating latex coating composition, more particularly, an aqueous dispersion of polymer particles functionalized with acetoacetoxyethyl groups and a CO 2 abating additive.
• Post film-forming curing of latex films is desirable to achieve improved hardness, as well as chemical-, scrub-, dirt-pickup-, and print resistance in the final coating.
• polymeric binder particles functionalized with acetoacetoxyethyl methacrylate (AAEM) has been a mainstay for ambient cure of architectural coatings. AAEM has relatively low toxicity and undergoes oxidative crosslinking efficiently to provide an excellent balance of properties in the final coating.
• the present invention addresses a need by providing, in a first aspect, a composition
• a composition comprising a) an aqueous dispersion of acrylic-based polymer particles functionalized with from 1 to 20 weight percent structural units of an acetoacetoxy functionalized monomer, based on the weight of the polymer particles; and b) an additive which is a compound functionalized with 1 to 4 non-hindered primary amine groups and having a boiling point of at least 250 °C and an equivalent molecular weight of not more than 1100 g/mole; wherein the composition comprises a substantial absence of ammonium cation; the mole:mole ratio of non-hindered primary amine groups to structural units of the acetoacetoxy functionalized monomer is from 0.4 to 5, and the pH of the composition is greater than 7.
• the composition of the present invention is effective for abating CO 2 in latex compositions functionalized with structural units of an acetoacetoxy containing monomer such as AAEM.
• the present invention is a process for forming a CO 2 abating composition
• a process for forming a CO 2 abating composition comprising the step of contacting an aqueous dispersion of acrylic-based polymer particles comprising 1 to 20 weight percent structural units of an acetoacetoxy functionalized monomer, based on the weight of the polymer particles, with an additive which is a compound functionalized with 1 to 4 non-hindered primary amine groups and having a boiling point of at least 250 °C and an equivalent molecular weight of not more than 1100 g/mole to form a CO 2 abating composition; wherein substantially no ammonia or a generator of ammonia is added in the step.
• the present invention is a composition
• a composition comprising a) an aqueous dispersion of acrylic-based polymer particles functionalized with from 1 to 20 weight percent structural units of an acetoacetoxy functionalized monomer, based on the weight of the polymer particles; and b) an additive which is a compound functionalized with 1 to 4 non-hindered primary amine groups and having a boiling point of at least 250 °C and an equivalent molecular weight of not more than 1100 g/mole; wherein the composition comprises a substantial absence of ammonium cation; the mole:mole ratio of non-hindered primary amine groups to structural units of the acetoacetoxy functionalized monomer is from 0.4 to 5, and the pH of the composition is greater than 7.
• structural unit of the named monomer refers to the remnant of the monomer after polymerization.
• a structural unit of methyl methacrylate is illustrated: where the dotted lines represent the points of attachment of the structural unit to the polymer backbone.
• a structural unit of acetoacetoxyethyl methacrylate is represented as follows:
• acrylic-based polymer particles is used herein to refer to polymer particles that comprise at least 30 weight percent, based on the weight of the polymer particles, structural units of one or more methacrylate monomers such as methyl methacrylate and ethyl methacrylate, and/or one or more acrylate monomers such as ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate.
• methacrylate monomers such as methyl methacrylate and ethyl methacrylate
• acrylate monomers such as ethyl acrylate, butyl acrylate, 2-propylheptyl acrylate, and 2-ethylhexyl acrylate.
• the acrylic-based polymer particles may also include structural units of acid monomers such as acrylic acid, methacrylic acid, and itaconic acid, as well as other non-acrylate or methacrylate monomers such as styrene, sulfur acid monomers such as 4-vinylbenzenesulfonic acid or a salt thereof, and phosphorus acid monomers such as phosphoethyl methacrylate or a salt thereof.
• acid monomers such as acrylic acid, methacrylic acid, and itaconic acid
• other non-acrylate or methacrylate monomers such as styrene
• sulfur acid monomers such as 4-vinylbenzenesulfonic acid or a salt thereof
• phosphorus acid monomers such as phosphoethyl methacrylate or a salt thereof.
• an acetoacetoxy functionalized monomer is a monomer capable of copolymerizing with an acrylate or methacrylate under emulsion polymerization conditions to form a copolymer comprising acetoacetoxy functionality.
• Preferred acetoacetoxy functionalized monomers are acetoacetoxy-C 1 -C 4 -alkyl acrylates, methacrylates, and acrylamides, examples of which include AAEM, acetoacetoxyethyl acrylate, acetoacetoxyethyl acrylamide, acetoacetoxyethyl methacrylamide, acetoacetoxypropyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl acrylate, and acetoacetoxybutyl methacrylate, with AAEM being preferred.
• the aqueous dispersion of acrylic based polymer particles comprises from 1 to 15, more preferably from 1 to 10 weight percent structural units of an acetoacetoxy functionalized monomer, more preferably AAEM.
• equivalent molecular weight is used herein to refer to the molecular weight of the additive divided by the number of amine groups per molecule.
• the equivalent molecular weight of the additive is not greater than 500 g/mole, more preferably from 100 to 500 g/mole.
• the term "substantial absence of ammonium cation" means that the composition comprises less than that concentration of ammonium cation, arising from the addition of ammonia or a generator of ammonia (for example, NH 4 OH or NH 4 HCO 3 ), that would be required to bring the pH of the composition to greater than 7, more preferably to greater than 6, in the absence of the additive.
• the composition comprises not greater than 0.1, more preferably not greater than 0.01, more preferably not greater than 0.001, and most preferably 0 moles of ammonium cation per mole of amine group in the additive.
• non-hindered primary amine refers to a primary amine that is bonded to a secondary or tertiary carbon atom, but not a quaternary carbon atom.
• the non-hindered primary amine is water miscible, more preferably a water-miscible liquid: That is, the non-hindered primary amine more preferably is a liquid that forms a single phase with water in the proportions used.
• suitable water-miscible primary amines are water-miscible polyetheramines, which are compounds that contain one or more of the following functional group: where each R is independently H or methyl; and x is 2 to 22.
• Preferred polyetheramines are mono-, di-, tri-, or tetrafunctional polyetheramines, more preferably mono-, di-, or trifunctional polyetheramines.
• polyethermonoamines An example of a subclass of polyethermonoamines is represented by the following structure: where each R is independently H or methyl and m is from 5 to 22, with the proviso that the equivalent molecular weight does not exceed 1100 g/mole.
• Examples of subclasses of polyetherdiamines are represented by the following structures: where n is from 2 to 40, more preferably to 20, and most preferably to 7; and where p + q is from 1 to 6, and r is from 2 to 13.
• water-miscible primary amines examples include 3,3'-(ethane-1,2-diylbis(oxy))bis(propan-1-amine); 4,9-dioxadodecane-1,12-diamine; 4,9-dioxadodecane-1,12-diamine; 4,7-dioxadodecane-1,10-diamine; and 4,7,10-trioxatridecane-1,13-diamine.
• suitable polyetheramines are JEFFAMINE D-230, D-400, D-2000, M-600, M-1000, ED-600, ED-900, T-403, and T-3000 polyetheramines.
• the aqueous dispersion of the acetoacetoxy functionalized copolymer particles (the latex) are advantageously blended with the additive to make the composition; preferably the mole:mole ratio of the primary amine groups in the additive to the structural units of the acetoacetoxy monomer is from 0.6 to 2.
• the pH of the composition is preferably at least 7.5, more preferably at least 8.0; and preferably not more than 11.
• the present invention is a process for forming a CO 2 abating composition
• a process for forming a CO 2 abating composition comprising the step of contacting an aqueous dispersion of acrylic-based polymer particles comprising 1 to 20 weight percent structural units of an acetoacetoxy functionalized monomer, based on the weight of the polymer particles, with an additive which is a compound functionalized with 1 to 4 non-hindered primary amine groups; and having a boiling point of at least 250 °C and an equivalent molecular weight of not more than 1100 g/mole to form a CO 2 abating composition; wherein substantially no ammonia or a generator of ammonia is added in the step.
• the term "substantially no ammonia or generator of ammonia” means that the amount of ammonia or generator of ammonia (e.g., NH 4 OH or NH 4 HCO 3 ) that is added is less than the amount that would be required to bring the pH of the composition to greater than 7, more preferably to greater than 6, in the absence of the additive.
• the amount of ammonia or generator of ammonia e.g., NH 4 OH or NH 4 HCO 3
• the amount of ammonia or generator of ammonia e.g., NH 4 OH or NH 4 HCO 3
• the amount of ammonia or generator of ammonia e.g., NH 4 OH or NH 4 HCO 3
• the amount of ammonia or generator of ammonia e.g., NH 4 OH or NH 4 HCO 3
• composition of the present invention is useful in coatings formulations and is advantageously combined with one or more of the following materials: pigments, such as TiO 2 and opaque polymers; defoamers; surfactants; dispersants; rheology modifiers; coalescents; and neutralizing agents.
• a first monomer emulsion (ME1) was prepared by first mixing together deionized water (144.6 g), RHODAFACTM RS-610/A25 surfactant (34.9 g), and Polystep B-11 surfactant (5.8 g), then admixing, in the following order, butyl acrylate (349.0 g), methyl methacrylate (419.9 g), allyl methacrylate (4.2 g), and methacrylic acid (3.9 g).
• a second monomer emulsion was prepared by mixing deionized water (304.9 g) with RHODAFAC RS-610/A25 (99.3 g), then admixing, in the following order, butyl acrylate (407.2 g), methyl methacrylate (633.6 g), AAEM (87.3 g), and methacrylic acid (35.1 g).
• a co-feed solution of sodium persulfate (1.8 g) in deionized water (105.0 g) was fed to the flask over a period of 125 min. After onset of addition of the co-feed, the remainder of ME1 was fed to the reactor over 50 min. Upon completion of addition of ME1, a 45-mL rinse was added to the reactor and the reaction was held at 85 °C for 5 min.
• ME2 was fed to the reactor over 70 min, after which time a 30-mL rinse was added to the reactor.
• the reaction was maintained at 85 °C for 10 min hold before cooling to 65 °C.
• a promoter solution of ferrous sulfate heptahydrate (0.011 g) in water (20 mL) was prepared and added to the reactor.
• a solution of 70% aqueous t -butyl hydroperoxide (0.84 g) and deionized water (21.1 mL); and a solution of isoascorbic acid (0.64 g) in water (21.3 mL) were fed separately and concurrently to the reactor over 30 min to chase residual monomers.
• the reactor was cooled during which time a 10% aqueous solution of potassium carbonate (113 g) was added to the reactor over a period of 3 min.
• ROCIMATM BT2S biocide (A Trademark of The Dow Chemical Company or Its affiliates, 10.3 g) in water (20 mL) was added to the reactor when the reactor temperature dropped below 30 °C.
• the resulting dispersion was filtered through a 325 mesh screen after the contents were cooled to room temperature. The solids content was found to be 44.7%.
• Binders passing heat age were also tested for minimum film formation temperature (MFFT) to ensure that pre-crosslinking was not occurring to such an extent that hindered film formation.
• Table 1 shows the effect of various additives on pressure buildup. MFFT o refers to the initial minimum film formation temperature prior to heat aging.
• D-230 and D-400 refer to Jeffamine D-230 ( z ⁇ to 2.5) and D-400 (z ⁇ to 6.1) polyetheramines (obtained from Huntsman), which are characterized by the following structure: Table 1 - Effect of Base Additive on Gassing Ex. No. Additive (% blinder solids) Gassing MFFT o MFFT after 14 d, 60 °C Comp. 1 None Failure 23 °C NA Comp. 2 Ethomeen 2.5 Failure 23 °C NA 1 D-230 1.4 Pass 23 °C 25 °C 2 D-400 2.4 Pass 23 °C 23 °C
• the MFFT after heat age testing was substantially the same as the MFFT o for the Examples as well as the comparative examples, which shows that the additive does not adversely impact film formation.
• the examples of the present invention have been found to control pressure building in a paint can. Without the polyetheramine additive, unacceptable pressure buildup occurs and even occurs with the addition of the tertiary amine. It has further been discovered that coatings formulations prepared using the composition of the present invention maintain acceptable performance in the substantial absence of an ammonia neutralizer, preferably in the total absence of an ammonia neutralizer.

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• Organic Chemistry (AREA)
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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Wood Science & Technology (AREA)
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• 2016
  • 2016-03-29 EP EP16162631.2A patent/EP3085713A1/fr not_active Withdrawn
  • 2016-04-04 AU AU2016202072A patent/AU2016202072A1/en not_active Abandoned
  • 2016-04-05 CA CA2926130A patent/CA2926130A1/fr not_active Abandoned
  • 2016-04-08 CN CN201610218282.1A patent/CN106065248A/zh active Pending
  • 2016-04-11 KR KR1020160044146A patent/KR20160125290A/ko not_active Withdrawn
  • 2016-04-11 BR BR102016008034A patent/BR102016008034A2/pt not_active IP Right Cessation
  • 2016-04-18 US US15/131,618 patent/US20160312047A1/en not_active Abandoned

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